JPH0128935B2 - - Google Patents
Info
- Publication number
- JPH0128935B2 JPH0128935B2 JP57065006A JP6500682A JPH0128935B2 JP H0128935 B2 JPH0128935 B2 JP H0128935B2 JP 57065006 A JP57065006 A JP 57065006A JP 6500682 A JP6500682 A JP 6500682A JP H0128935 B2 JPH0128935 B2 JP H0128935B2
- Authority
- JP
- Japan
- Prior art keywords
- photosensitive
- film
- solution
- mercaptobenzothiazole
- positive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 22
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical group [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 13
- YEDUAINPPJYDJZ-UHFFFAOYSA-N 2-hydroxybenzothiazole Chemical compound C1=CC=C2SC(O)=NC2=C1 YEDUAINPPJYDJZ-UHFFFAOYSA-N 0.000 claims description 7
- UDATXMIGEVPXTR-UHFFFAOYSA-N 1,2,4-triazolidine-3,5-dione Chemical compound O=C1NNC(=O)N1 UDATXMIGEVPXTR-UHFFFAOYSA-N 0.000 claims description 5
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 5
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 claims description 5
- CLEJZSNZYFJMKD-UHFFFAOYSA-N 3h-1,3-oxazole-2-thione Chemical compound SC1=NC=CO1 CLEJZSNZYFJMKD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- ZEMGGZBWXRYJHK-UHFFFAOYSA-N thiouracil Chemical compound O=C1C=CNC(=S)N1 ZEMGGZBWXRYJHK-UHFFFAOYSA-N 0.000 claims description 5
- 229950000329 thiouracil Drugs 0.000 claims description 5
- UMURLIQHQSKULR-UHFFFAOYSA-N 1,3-oxazolidine-2-thione Chemical compound S=C1NCCO1 UMURLIQHQSKULR-UHFFFAOYSA-N 0.000 claims description 4
- LOCAIGRSOJUCTB-UHFFFAOYSA-N indazol-3-one Chemical compound C1=CC=C2C(=O)N=NC2=C1 LOCAIGRSOJUCTB-UHFFFAOYSA-N 0.000 claims description 3
- -1 mercaptovirimidine Chemical compound 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 206010034972 Photosensitivity reaction Diseases 0.000 description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 230000036211 photosensitivity Effects 0.000 description 4
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical compound SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- SWEICGMKXPNXNU-UHFFFAOYSA-N 1,2-dihydroindazol-3-one Chemical compound C1=CC=C2C(O)=NNC2=C1 SWEICGMKXPNXNU-UHFFFAOYSA-N 0.000 description 2
- CWIYBOJLSWJGKV-UHFFFAOYSA-N 5-methyl-1,3-dihydrobenzimidazole-2-thione Chemical compound CC1=CC=C2NC(S)=NC2=C1 CWIYBOJLSWJGKV-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 229940074391 gallic acid Drugs 0.000 description 2
- 235000004515 gallic acid Nutrition 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 229940079877 pyrogallol Drugs 0.000 description 2
- 150000003459 sulfonic acid esters Chemical class 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- KGWYICAEPBCRBL-UHFFFAOYSA-N 1h-indene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)C=CC2=C1 KGWYICAEPBCRBL-UHFFFAOYSA-N 0.000 description 1
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 1
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 1
- KLIDCXVFHGNTTM-UHFFFAOYSA-N 2,6-dimethoxyphenol Chemical compound COC1=CC=CC(OC)=C1O KLIDCXVFHGNTTM-UHFFFAOYSA-N 0.000 description 1
- JQCWLRHNAHIIGW-UHFFFAOYSA-N 2,8-dimethylnonan-5-one Chemical compound CC(C)CCC(=O)CCC(C)C JQCWLRHNAHIIGW-UHFFFAOYSA-N 0.000 description 1
- XXXFZKQPYACQLD-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl acetate Chemical compound CC(=O)OCCOCCO XXXFZKQPYACQLD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical group [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- CDNHLXOFELOEOL-UHFFFAOYSA-N 3-methyl-1h-benzimidazole-2-thione Chemical compound C1=CC=C2N(C)C(S)=NC2=C1 CDNHLXOFELOEOL-UHFFFAOYSA-N 0.000 description 1
- YLISVVKTUVAGCN-UHFFFAOYSA-N 4-hydroxy-1,2,4-triazolidine-3,5-dione Chemical compound ON1C(=O)NNC1=O YLISVVKTUVAGCN-UHFFFAOYSA-N 0.000 description 1
- XJOOWWMZMXBLAO-UHFFFAOYSA-N 4-methyl-1,2,4-triazolidine-3,5-dione Chemical compound CN1C(=O)NNC1=O XJOOWWMZMXBLAO-UHFFFAOYSA-N 0.000 description 1
- GOSUFRDROXZXLN-UHFFFAOYSA-N 4-phenyl-1,2,4-triazolidine-3,5-dione Chemical compound O=C1NNC(=O)N1C1=CC=CC=C1 GOSUFRDROXZXLN-UHFFFAOYSA-N 0.000 description 1
- FFQWZJULSCUVRK-UHFFFAOYSA-N 5,6-dimethyl-3h-1,3-benzothiazole-2-thione Chemical compound C1=C(C)C(C)=CC2=C1SC(=S)N2 FFQWZJULSCUVRK-UHFFFAOYSA-N 0.000 description 1
- ZZIHEYOZBRPWMB-UHFFFAOYSA-N 5-chloro-1,3-dihydrobenzimidazole-2-thione Chemical compound ClC1=CC=C2NC(S)=NC2=C1 ZZIHEYOZBRPWMB-UHFFFAOYSA-N 0.000 description 1
- NOVHYVKPKWACML-UHFFFAOYSA-N 5-chloro-3h-1,3-benzothiazol-2-one Chemical compound ClC1=CC=C2SC(O)=NC2=C1 NOVHYVKPKWACML-UHFFFAOYSA-N 0.000 description 1
- NKYDKCVZNMNZCM-UHFFFAOYSA-N 5-chloro-3h-1,3-benzothiazole-2-thione Chemical compound ClC1=CC=C2SC(S)=NC2=C1 NKYDKCVZNMNZCM-UHFFFAOYSA-N 0.000 description 1
- BOBIZYYFYLLRAH-UHFFFAOYSA-N 5-chloro-3h-1,3-benzoxazole-2-thione Chemical compound ClC1=CC=C2OC(S)=NC2=C1 BOBIZYYFYLLRAH-UHFFFAOYSA-N 0.000 description 1
- FKCOGUDKADCPIB-UHFFFAOYSA-N 5-chloroindazol-3-one Chemical compound ClC1=CC=C2N=NC(=O)C2=C1 FKCOGUDKADCPIB-UHFFFAOYSA-N 0.000 description 1
- DFKVVBOVTVBURY-UHFFFAOYSA-N 5-hydroxy-1,3-dihydrobenzimidazole-2-thione Chemical compound OC1=CC=C2NC(S)=NC2=C1 DFKVVBOVTVBURY-UHFFFAOYSA-N 0.000 description 1
- CHCYXBPFWCRKIT-UHFFFAOYSA-N 5-methyl-3h-1,3-benzothiazol-2-one Chemical compound CC1=CC=C2SC(=O)NC2=C1 CHCYXBPFWCRKIT-UHFFFAOYSA-N 0.000 description 1
- PSVWPGOECLDBAN-UHFFFAOYSA-N 5-methylindazol-3-one Chemical compound CC1=CC=C2N=NC(=O)C2=C1 PSVWPGOECLDBAN-UHFFFAOYSA-N 0.000 description 1
- YPXQSGWOGQPLQO-UHFFFAOYSA-N 5-nitro-1,3-dihydrobenzimidazole-2-thione Chemical compound [O-][N+](=O)C1=CC=C2N=C(S)NC2=C1 YPXQSGWOGQPLQO-UHFFFAOYSA-N 0.000 description 1
- NFZDOFMXGCPMCX-UHFFFAOYSA-N 5-nitro-3h-1,3-benzothiazole-2-thione Chemical compound [O-][N+](=O)C1=CC=C2SC(=S)NC2=C1 NFZDOFMXGCPMCX-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- HOASVNMVYBSLSU-UHFFFAOYSA-N 6-ethoxy-3h-1,3-benzothiazole-2-thione Chemical compound CCOC1=CC=C2N=C(S)SC2=C1 HOASVNMVYBSLSU-UHFFFAOYSA-N 0.000 description 1
- MVFGOAOKHXOETI-UHFFFAOYSA-N 6-ethoxy-3h-1,3-benzoxazole-2-thione Chemical compound CCOC1=CC=C2N=C(S)OC2=C1 MVFGOAOKHXOETI-UHFFFAOYSA-N 0.000 description 1
- NUMDWMDMUXZMHA-UHFFFAOYSA-N 6-methyl-3h-1,3-benzoxazole-2-thione Chemical compound CC1=CC=C2NC(=S)OC2=C1 NUMDWMDMUXZMHA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
Description
本発明は、ポジ型画像の形成方法、さらに詳し
くは、キノンジアジド基含有化合物と特殊な増感
剤との新規な組合せを感光性成分とした高感度ポ
ジ型感光性組成物を使用したポジ型画像の形成方
法に関するものである。
従来、キノンジアジド基含有化合物にポジフイ
ルムマスクを介して紫外線を照射すると、弱アル
カリ性水溶液に可溶なインデンカルボン酸に変わ
ることが知られており、この性質を利用してキノ
ンジアジド基含有化合物がポジ型感光性材料に広
く用いられている。
キノンジアジド基含有化合物は、通常被膜形成
用のフエノール樹脂などと混合して用いられるこ
とが多く、また直接フエノール樹脂をキノンジア
ジド基含有化合物のスルホン酸エステルとして化
学的に結合させたものも用いられている。
このように、キノンジアジド基含有化合物は被
膜形成物質と組み合わせてポジ型感光性材料とし
て広く使用されているが、紫外線の比較的長い照
射時間を必要とするため画像形成工程に時間がか
かり、画像形成の作業性が悪いという問題点を有
しており、その感度の向上が大きな課題となつて
いる。特に、近年LSI、超LSIなどの半導体デバ
イス及び感光性印刷版の製造において、その画像
形成工程（ホトリソグラフイー）の紫外線照射時
間の短縮、すなわちポジ型感光性材料の感度の増
感が強く要求されるようになり、大巾な改善が望
まれている。
このような課題に対し、キノンジアジド基含有
化合物自体について、あるいはこれと組み合わさ
れる各種樹脂の選択など、多くの改良研究が行わ
れているが、まだ満足すべき感度を得るには至つ
ていない。
本発明者らは、キノンジアジド基含有化合物の
感度を上昇させる有効な増感剤を開発すること
で、作業性に優れたポジ型画像の形成方法の提供
を目的として、鋭意研究の結果、ある種の含窒素
複素環化合物を用いることによりその目的を達成
しうることを見出し、本発明をなすに至つた。
すなわち、本発明は、(イ)キノンジアジド基含有
化合物と、(ロ)メルカプトオキサゾール、メルカプ
トベンゾキサゾール、メルカプトオキサゾリン、
メルカプトベンゾチアゾール、ベンゾチアゾロ
ン、メルカプトベンゾイミダゾール、ウラゾー
ル、チオウラシル、メルカプトピリミジン、イン
ダゾロン及びそれらの誘導体の中から選ばれた少
なくとも１種との組合せを感光性成分としたポジ
型感光性組成物を基板上に塗布し、乾燥したの
ち、活性光線を選択的に照射し、現像することを
特徴とするポジ型画像の形成方法を提供するもの
である。
本発明方法で使用されるポジ型感光性組成物の
(イ)成分として用いられる化合物はキノンジアジド
基含有化合物であつて、オルトベンゾキノンジア
ジド、オルトナフトキノンジアジド、オルトアン
トラキノンジアジド及び例えばオルトナフトキノ
ンジアジドスルホン酸エステル類などのようなこ
れらの核置換誘導体が含まれ、またオルトキノン
ジアジドスルホニルクロリドと水酸基又はアミノ
基をもつ化合物、例えばフエノール、ｐ−メトキ
シフエノール、ジメチルフエノール、ヒドロキノ
ン、ビスフエノールＡ、ナフトール、ピロカテコ
ール、ピロガロール、ピロガロールモノメチルエ
ーテル、ピロガロール−１，３−ジメチルエーテ
ル、没食子酸、水酸基を一部残しエステル化又は
エーテル化された没食子酸、アニリン、ｐ−アミ
ノジフエニルアミンなどとの反応生成物なども包
含される。
本発明方法で使用されるポジ型感光性組成物に
おいて、上記感光性物質の(イ)成分と組み合わせて
用いる(ロ)成分は、メルカプトオキサゾール、メル
カプトベンゾキサゾール、メルカプトオキサゾリ
ン、メルカプトベンゾチアゾール、ベンゾチアゾ
ロン、メルカプトベンゾイミダゾール、ウラゾー
ル、チオウラシル、メルカプトピリミジン、イン
ダゾロン及びそれらの誘導体が包含され、これら
の化合物は、縮合環を有するもの、低級アルキル
基、ニトロ基、アミノ基、ヒドロキシル基、アル
コキシ基、フエニル基及びハロゲン原子などの置
換基をもつものであつてもよい。これら増感剤(ロ)
成分の具体的な例としては、例えば２−メルカプ
トベンゾキサゾール、５−クロロ−２−メルカプ
トベンゾキサゾール、６−エトキシ−２−メルカ
プトベンゾキサゾール、６−メチル−２−メルカ
プトベンゾキサゾール、２−メルカプトオキサゾ
リン、２−メルカプトベンゾチアゾール、６−エ
トキシ−２−メルカプトベンゾチアゾール、５−
クロロ−２−メルカプトベンゾチアゾール、、５，
６−ジメチル−２−メルカプトベンゾチアゾー
ル、２−メルカプト−５−ニトロベンゾチアゾー
ル、ベンゾチアゾロン、５−クロロ−２−ベンゾ
チアゾロン、５−メチル−２−ベンゾチアゾロ
ン、２−メルカプトベンゾイミダゾール、５−メ
チル−２−メルカプトベンゾイミダゾール、６−
メチル−２−メルカプトベンゾイミダゾール、５
−クロロ−２−メルカプトベンゾイミダゾール、
２−メルカプト−５−ニトロベンゾイミダゾー
ル、５−ヒドロキシ−２−メルカプトベンゾイミ
ダゾール、１−メチル−２−メルカプトベンゾイ
ミダゾール、ウラゾール、４−フエニルウラゾー
ル、４−メチルウラゾール、４−ヒドロキシウラ
ゾール、チオウラシル、２−メルカプトオキサゾ
ール、２−メルカプトピリミジン、３−インダゾ
ロン、５−メチル−３−インダゾロン、５−クロ
ロ−３−インダゾロンなどを挙げることができ
る。
これらの(ロ)成分は、キノンジアジド基含有化合
物及び被膜形成物質の100重量部当り0.1〜25重量
部の割合で用いることが効果的であり、好ましい
使用量は0.5〜20重量部である。あまり少なすぎ
ると増感効果が得られないし、あまり多すぎても
使用量に見合う増感効果が得られないので不経済
である。その最適使用量は使用するキノンジアジ
ド基含有化合物及び増感剤の組み合わせにより変
動するが、簡単な実験により容易に決定すること
ができる。
本発明方法で使用されるポジ型感光性組成物に
おける被膜形成用物質としては、アルカリ可溶性
樹脂が好ましく用いられ、それらの具体的な例と
しては、フエノール又はクレゾールなどとアルデ
ヒド類から製造されるノボラツク樹脂、ポリビニ
ルアルコール、ポリビニルアルキルエーテル、ス
チレンとアクリル酸との共重合体、メタクリル酸
とメタクリル酸アルキルエステルとの共重合体、
ヒドロキシスチレンの重合体、ポリビニルヒドロ
キシベンゾエート、ポリビニルヒドロキシベンザ
ールなどを挙げることができる。
被膜形成物質は、キノンジアジド基含有化合物
の10重量部に対して100重量部以下、好ましい使
用量は55重量部以下である。被膜形成物質があま
り多すぎると得られる画像のマスクパターン忠実
性が劣り転写性が悪くなる。キノンジアジド基含
有化合物が被膜形成用として使用されるフエノー
ル樹脂などと化学的に結合していない場合には、
被膜形成物質を配合して用いることが望ましく、
そのときの被膜形成物質はキノンジアジド基含有
化合物10重量部に対して25重量部以上配合するの
が良い。それよりも少ない場合には、塗膜の均一
性が悪く解像力も落ちる。
本発明方法で使用されるポジ型感光性組成物
は、適当な溶剤に前記した(イ)成分のキノンジアジ
ド基含有化合物と(ロ)成分の増感剤を溶解し、さら
に前記した被膜形成用物質を溶解した溶液の形で
用いるのが有利である。
このような溶剤の例としては、アセトン、メチ
ルエチルケトン、シクロヘキサノン、イソアミル
ケトンなどのケトン類：エチレングリコール、エ
チレングリコールモノアセテート、ジエチレング
リコール又はジエチレングリコールモノアセテー
トのモノメチルエーテル、モノエチルエーテル、
モノプロピルエーテル、モノブチルエーテル又は
モノフエニルエーテルなどの多価アルコール類及
びその誘導体：ジオキサンのような環式エーテル
類：及び酢酸メチル、酢酸エチル、酢酸ブチルな
どのエステル類を挙げることができる。これらは
単独で用いてもよいし、また２種以上混合して用
いてもよい。
本発明方法で使用されるポジ型感光性組成物に
は、さらに相溶性のある添加物、例えば付加的樹
脂、可塑剤、安定剤あるいは現像した像をより一
層可視的にするための着色料などの慣用されてい
るものを添加含有させることができる。
本発明の組成物の好適な使用方法について一例
を示せば、さず例えばシリコンウエハーのような
基板上にキノンジアジド基含有化合物及び前記し
た増感剤を、例えばフエノールノボラツク樹脂と
ともに前記したような適当な溶剤に溶かした溶液
をスピンナー等で塗布し、乾燥して感光層を形成
させる。しかる後、紫外線を発光する光源、例え
ば低圧水銀灯、高圧水銀灯、超高圧水銀灯、アー
ク灯、キセノンランプなどを用い所要のマスクパ
ターンを介して露光するか、あるいは電子線を走
査しながら照射する。次にこれを現像液、例えば
１〜２重量％水酸化ナトリウム水溶液のような弱
アルカリ性水溶液に浸せきすると、露光によつて
可溶化した部分が選択的に溶解除去されマスクパ
ターンに忠実な画像を得ることができる。
本発明は、ポジ型感光性組成物の感度が著しく
高められているので、従来よりも紫外線を露光し
て画像を形成させるのに要する時間が短縮され、
作業性の向上した高い実用的価値を有するポジ型
画像の形成方法である。
次に実施例により本発明をさらに詳細に説明す
る。
比較例 １
エチレングリコールモノエチルエーテルアセテ
ート75ｇに没食子酸ｎ−プロピルエステルのナフ
トキノン−（１，２）−ジアジド−(2)−５−スルホ
ン酸トリエステル５ｇとフエノールノボラツク樹
脂20ｇとを溶解し、これをろ過して感光膜形成用
感光液を調製した。この液をスピンナーを用いて
アルミニウム基板上に塗布し80〜90℃に保温され
ている乾燥機中に30分間入れて乾燥し、膜厚1.0μ
ｍの感光塗膜を得た。この膜に超高圧水銀灯露光
装置（キヤノン社製PLA−300）を用い、マスク
パターンを介して露光し、1.5％水酸化ナトリウ
ム水溶液で現像した。露光においてマスクパター
ンを忠実に再現して画像を形成するに要する最小
露光時間（以下これを適性露光時間という）は
5.2秒であつた。
実施例 １
比較例１と同様にして感光液を調製し、この液
にベンゾチアゾロン２ｇを添加溶解後ろ過して新
たな感光液を調製した。この感光液をスピンナー
を用いてアルミニウム基板上に塗布し80〜90℃に
保温されている乾燥機中に30分間入れて膜厚1.0μ
ｍの感光塗膜を得た。続いてマスクパターンを介
してPLA−300を用い同様に感光膜に露光後1.5％
水酸化ナトリウム水溶液を現像液として現像し
た。このポジ型感光膜の適性露光時間は3.4秒で
あり、比較例１と比較すればベンゾチアゾロンが
優れた増感作用を有することがわかる。
実施例 ２
実施例１におけるベンゾチアゾロンに代えて２
−メルカプトベンゾキサゾールを増感剤として用
い適性露光時間を求めたところ3.2秒であつた。
この感光性組成物は比較例１に比べて約1.5倍高
い感光度を示した。
比較例 ２
２，３，４−トリヒドロキシベンゾフエノンの
ナフトキノン−（１，２）−ジアジド−(2)−５−ス
ルホン酸ジエステル５ｇとｍ−クレゾールノボラ
ツク樹脂20ｇとをエチレングリコールモノエチル
エーテルアセテート70ｇに溶解し、ろ過して感光
液を調製した。この感光液をシリコンウエハー上
にスピンナーを用いて塗布し80〜90℃に保持され
た乾燥機の中に30分間入れて厚さ1.4μｍの感光塗
膜を得た。続いて比較例１と同様にマスクパター
ンを介して露光後、1.8％水酸化ナトリウム水溶
液で現像し、マスクパターンに忠実な1.0μｍを解
像する画像を得た。この感光膜は適性露光時間は
3.2秒であつた。
実施例 ３
比較例２と同様にして感光液を調製し、この液
に２−メルカプトベンゾチアゾール２ｇを入れ溶
解後、ろ過して感光液を調製した。この感光液を
スピンナーを用いてシリコンウエハー上に塗布
し、80〜90℃に保持された乾燥機中に30分間入れ
て膜厚1.4μｍの感光塗膜を得た。続いて、この膜
にマスクパターンを介してPLA−300を用い露光
した後、1.8％水酸化ナトリウム水溶液を現像液
として現像した。このときの適性露光時間は2.2
秒であり、比較例２と比較すると、２−メルカプ
トベンゾチアゾールが増感剤として有効に作用し
ていることがわかる。
実施例 ４
実施例３の２−メルカプトベンゾチアゾールの
量を２ｇから４ｇに増量して実施例３と同様に操
作したところ、適性露光時間は1.6秒であつた。
２−メルカプトベンゾチアゾール量の増大により
感光性がいつそう高められ、増感剤として極めて
効果的に作用していることが認められた。
実施例 ５
実施例３の２−メルカプトベンゾチアゾールの
添加量を1.2ｇにして実施例３と同様に操作した
ところ、適性露光時間は2.6秒であつた。この場
合にも２−メルカプトベンゾチアゾールの増感剤
としての効果が充分認められた。
実施例 ６
実施例３の２−メルカプトベンゾチアゾールに
代えてウラゾール２ｇを用い適性露光時間を求め
たところ2.0秒であつた。この感光組成物は比較
例２のものに比べて約1.5倍の感光度を有する。
実施例 ７
実施例３の２−メルカプトベンゾチアゾールに
代えて２−メルカプトピリミジン２ｇを用い適性
露光時間を求めたところ2.0秒であつた。
実施例 ８
比較例２と同様にして感光液を調製し、この感
光液に、増感剤として２−メルカプトオキサゾー
ル、２−メルカプトベンゾイミダゾール、チオウ
ラシル又は３−インダゾロンをそれぞれ1.2ｇ添
加し溶解後、ろ過して各感光液を調製した。そし
て比較例２と同様にそれぞれ感光塗膜を形成し、
露光および現像処理して、各増感剤を含有してな
る感光性組成物の適性露光時間を求めた。それら
の結果を次の表にまとめて示す。
The present invention relates to a method for forming a positive image, and more specifically, a positive image using a highly sensitive positive photosensitive composition containing a novel combination of a quinonediazide group-containing compound and a special sensitizer as a photosensitive component. This relates to a method of forming. Conventionally, it has been known that when a quinonediazide group-containing compound is irradiated with ultraviolet rays through a positive film mask, it turns into indenecarboxylic acid, which is soluble in a weakly alkaline aqueous solution.Using this property, the quinonediazide group-containing compound can be converted into a positive type. Widely used in photosensitive materials. Quinonediazide group-containing compounds are often used by mixing them with phenolic resins for film formation, and compounds in which phenolic resins are directly chemically bonded as sulfonic acid esters of quinonediazide group-containing compounds are also used. . As described above, quinonediazide group-containing compounds are widely used as positive photosensitive materials in combination with film-forming substances, but the image forming process is time-consuming due to the relatively long irradiation time of ultraviolet rays. The problem is that the workability is poor, and improving the sensitivity has become a major issue. In particular, in recent years, in the production of semiconductor devices such as LSI and VLSI and photosensitive printing plates, there has been a strong demand for shortening the ultraviolet irradiation time in the image forming process (photolithography), that is, increasing the sensitivity of positive photosensitive materials. As a result, drastic improvements are desired. To address these issues, many improvements have been made on the quinonediazide group-containing compound itself or on the selection of various resins to be combined with it, but satisfactory sensitivity has not yet been achieved. The present inventors have developed an effective sensitizer that increases the sensitivity of quinonediazide group-containing compounds, and have developed a method for forming positive images with excellent workability. The inventors have discovered that the object can be achieved by using a nitrogen-containing heterocyclic compound, and have completed the present invention. That is, the present invention provides (a) a compound containing a quinonediazide group, and (b) a mercaptooxazole, a mercaptobenzoxazole, a mercaptooxazoline,
A positive photosensitive composition containing a combination of at least one selected from mercaptobenzothiazole, benzothiazolone, mercaptobenzimidazole, urazol, thiouracil, mercaptopyrimidine, indazolone and derivatives thereof as a photosensitive component is placed on a substrate. The present invention provides a method for forming a positive image, which comprises coating and drying, and then selectively irradiating with actinic rays and developing. The positive photosensitive composition used in the method of the present invention
The compound used as component (a) is a quinonediazide group-containing compound, and includes orthobenzoquinonediazide, orthonaphthoquinonediazide, orthoanthraquinonediazide, and nuclear-substituted derivatives thereof such as orthonaphthoquinonediazide sulfonic acid esters, Also, compounds having orthoquinonediazide sulfonyl chloride and a hydroxyl group or an amino group, such as phenol, p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol A, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, It also includes reaction products with gallic acid, gallic acid esterified or etherified with some hydroxyl groups remaining, aniline, p-aminodiphenylamine, and the like. In the positive photosensitive composition used in the method of the present invention, the component (B) used in combination with the component (A) of the photosensitive substance is mercaptooxazole, mercaptobenzoxazole, mercaptooxazoline, mercaptobenzothiazole, benzothiazolone. , mercaptobenzimidazole, urazole, thiouracil, mercaptopyrimidine, indazolone and their derivatives.These compounds include those having fused rings, lower alkyl groups, nitro groups, amino groups, hydroxyl groups, alkoxy groups, phenyl groups and may have a substituent such as a halogen atom. These sensitizers (b)
Specific examples of the components include 2-mercaptobenzoxazole, 5-chloro-2-mercaptobenzoxazole, 6-ethoxy-2-mercaptobenzoxazole, 6-methyl-2-mercaptobenzoxazole, 2-mercaptooxazoline, 2-mercaptobenzothiazole, 6-ethoxy-2-mercaptobenzothiazole, 5-
Chloro-2-mercaptobenzothiazole, 5,
6-dimethyl-2-mercaptobenzothiazole, 2-mercapto-5-nitrobenzothiazole, benzothiazolone, 5-chloro-2-benzothiazolone, 5-methyl-2-benzothiazolone, 2-mercaptobenzimidazole, 5-methyl-2- Mercaptobenzimidazole, 6-
Methyl-2-mercaptobenzimidazole, 5
-chloro-2-mercaptobenzimidazole,
2-Mercapto-5-nitrobenzimidazole, 5-hydroxy-2-mercaptobenzimidazole, 1-methyl-2-mercaptobenzimidazole, urazole, 4-phenylurazole, 4-methylurazole, 4-hydroxyurazole , thiouracil, 2-mercaptooxazole, 2-mercaptopyrimidine, 3-indazolone, 5-methyl-3-indazolone, 5-chloro-3-indazolone, and the like. It is effective to use these components (b) in an amount of 0.1 to 25 parts by weight per 100 parts by weight of the quinonediazide group-containing compound and film-forming substance, and the preferred amount used is 0.5 to 20 parts by weight. If it is too small, no sensitizing effect can be obtained, and if it is too large, a sensitizing effect commensurate with the amount used cannot be obtained, which is uneconomical. The optimum amount to be used varies depending on the combination of the quinonediazide group-containing compound and the sensitizer used, but can be easily determined by simple experiments. As the film-forming substance in the positive photosensitive composition used in the method of the present invention, alkali-soluble resins are preferably used, and specific examples thereof include novola resins produced from phenol or cresol and aldehydes. Resin, polyvinyl alcohol, polyvinyl alkyl ether, copolymer of styrene and acrylic acid, copolymer of methacrylic acid and methacrylic acid alkyl ester,
Examples include hydroxystyrene polymers, polyvinylhydroxybenzoate, and polyvinylhydroxybenzal. The film-forming substance is used in an amount of 100 parts by weight or less, preferably 55 parts by weight or less, per 10 parts by weight of the quinonediazide group-containing compound. If the amount of the film-forming substance is too large, the mask pattern fidelity of the resulting image will be poor and the transferability will be poor. If the quinonediazide group-containing compound is not chemically bonded to the phenolic resin used for film formation,
It is desirable to use a film-forming substance in combination,
At that time, the film-forming substance is preferably blended in an amount of 25 parts by weight or more per 10 parts by weight of the quinonediazide group-containing compound. If the amount is less than that, the uniformity of the coating film will be poor and the resolution will also be reduced. The positive photosensitive composition used in the method of the present invention is prepared by dissolving the quinonediazide group-containing compound as the component (a) and the sensitizer as the component (b) in a suitable solvent, and then adding the film-forming material as described above. Advantageously, it is used in the form of a solution. Examples of such solvents include ketones such as acetone, methyl ethyl ketone, cyclohexanone, isoamyl ketone; monomethyl ether, monoethyl ether of ethylene glycol, ethylene glycol monoacetate, diethylene glycol or diethylene glycol monoacetate;
Mention may be made of polyhydric alcohols and their derivatives such as monopropyl ether, monobutyl ether or monophenyl ether; cyclic ethers such as dioxane; and esters such as methyl acetate, ethyl acetate and butyl acetate. These may be used alone or in combination of two or more. The positive-working photosensitive composition used in the method of the invention may further contain compatible additives such as additional resins, plasticizers, stabilizers or colorants to make the developed image more visible. It is possible to add and contain commonly used materials. To give an example of a preferred method of using the composition of the present invention, first, a quinonediazide group-containing compound and the above-mentioned sensitizer are deposited on a substrate, such as a silicon wafer, together with a phenol novolak resin and a suitable material such as the above-mentioned one. A solution dissolved in a suitable solvent is applied using a spinner or the like, and dried to form a photosensitive layer. Thereafter, exposure is performed using a light source that emits ultraviolet rays, such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an arc lamp, a xenon lamp, etc., or irradiation is performed while scanning an electron beam. Next, when this is immersed in a developing solution, for example, a weakly alkaline aqueous solution such as a 1 to 2% by weight aqueous sodium hydroxide solution, the portions made solubilized by exposure are selectively dissolved and removed, resulting in an image faithful to the mask pattern. be able to. In the present invention, since the sensitivity of the positive photosensitive composition is significantly increased, the time required to form an image by exposing to ultraviolet rays is shorter than in the past.
This is a method for forming a positive image with improved workability and high practical value. Next, the present invention will be explained in more detail with reference to Examples. Comparative Example 1 5 g of naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid triester of gallic acid n-propyl ester and 20 g of phenol novolak resin were dissolved in 75 g of ethylene glycol monoethyl ether acetate. This was filtered to prepare a photosensitive solution for forming a photosensitive film. This solution was applied onto an aluminum substrate using a spinner and dried in a dryer kept at 80-90°C for 30 minutes, resulting in a film thickness of 1.0 μm.
A photosensitive coating film of m was obtained. This film was exposed to light through a mask pattern using an ultra-high pressure mercury lamp exposure device (PLA-300 manufactured by Canon Inc.), and developed with a 1.5% aqueous sodium hydroxide solution. The minimum exposure time required to faithfully reproduce the mask pattern and form an image during exposure (hereinafter referred to as the appropriate exposure time) is
It took 5.2 seconds. Example 1 A photosensitive solution was prepared in the same manner as in Comparative Example 1, and 2 g of benzothiazolone was added to this solution, dissolved, and filtered to prepare a new photosensitive solution. This photosensitive solution was applied onto an aluminum substrate using a spinner and placed in a dryer kept at 80 to 90℃ for 30 minutes to create a film thickness of 1.0μ.
A photosensitive coating film of m was obtained. Subsequently, the photoresist film was exposed to 1.5% using PLA-300 through a mask pattern.
Development was carried out using an aqueous sodium hydroxide solution as a developer. The appropriate exposure time for this positive photosensitive film was 3.4 seconds, and a comparison with Comparative Example 1 shows that benzothiazolone has an excellent sensitizing effect. Example 2 2 instead of benzothiazolone in Example 1
- Using mercaptobenzoxazole as a sensitizer, the appropriate exposure time was determined to be 3.2 seconds.
This photosensitive composition exhibited a photosensitivity approximately 1.5 times higher than that of Comparative Example 1. Comparative Example 2 5 g of naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid diester of 2,3,4-trihydroxybenzophenone and 20 g of m-cresol novolac resin were mixed with ethylene glycol monoethyl ether. A photosensitive solution was prepared by dissolving in 70 g of acetate and filtering. This photosensitive solution was applied onto a silicon wafer using a spinner and placed in a dryer maintained at 80 to 90° C. for 30 minutes to obtain a photosensitive coating film with a thickness of 1.4 μm. Subsequently, as in Comparative Example 1, after exposure through a mask pattern, development was performed with a 1.8% aqueous sodium hydroxide solution to obtain an image resolving 1.0 μm faithful to the mask pattern. The appropriate exposure time for this photosensitive film is
It took 3.2 seconds. Example 3 A photosensitive solution was prepared in the same manner as in Comparative Example 2, and 2 g of 2-mercaptobenzothiazole was dissolved in the solution, followed by filtration to prepare a photosensitive solution. This photosensitive solution was applied onto a silicon wafer using a spinner and placed in a dryer maintained at 80 to 90° C. for 30 minutes to obtain a photosensitive coating film with a thickness of 1.4 μm. Subsequently, this film was exposed to light using PLA-300 through a mask pattern, and then developed using a 1.8% aqueous sodium hydroxide solution as a developer. The appropriate exposure time at this time is 2.2
When compared with Comparative Example 2, it can be seen that 2-mercaptobenzothiazole acts effectively as a sensitizer. Example 4 When the same procedure as in Example 3 was performed except that the amount of 2-mercaptobenzothiazole in Example 3 was increased from 2 g to 4 g, the appropriate exposure time was 1.6 seconds.
It was found that the photosensitivity was greatly increased by increasing the amount of 2-mercaptobenzothiazole, and that it acted extremely effectively as a sensitizer. Example 5 When the same procedure as in Example 3 was performed except that the amount of 2-mercaptobenzothiazole added was 1.2 g, the appropriate exposure time was 2.6 seconds. In this case as well, the effect of 2-mercaptobenzothiazole as a sensitizer was fully recognized. Example 6 Using 2 g of urazole in place of 2-mercaptobenzothiazole in Example 3, the appropriate exposure time was determined to be 2.0 seconds. This photosensitive composition has a photosensitivity about 1.5 times that of Comparative Example 2. Example 7 Using 2 g of 2-mercaptopyrimidine in place of 2-mercaptobenzothiazole in Example 3, the appropriate exposure time was determined to be 2.0 seconds. Example 8 A photosensitive solution was prepared in the same manner as in Comparative Example 2. To this photosensitive solution, 1.2 g each of 2-mercaptooxazole, 2-mercaptobenzimidazole, thiouracil, or 3-indazolone was added as a sensitizer and dissolved. Each photosensitive solution was prepared by filtration. Then, a photosensitive coating film was formed in the same manner as in Comparative Example 2,
The appropriate exposure time of the photosensitive composition containing each sensitizer was determined by exposure and development. The results are summarized in the table below.
【表】
各物質は、キノンジアジド基含有感光性物質の
感光性を高める増感剤として有効に作用している
ことが明瞭に理解できる。[Table] It can be clearly seen that each substance effectively acts as a sensitizer to increase the photosensitivity of the quinonediazide group-containing photosensitive material.
Claims (1)
プトオキサゾール、メルカプトベンゾキサゾー
ル、メルカプトオキサゾリン、メルカプトベンゾ
チアゾール、ベンゾチアゾロン、メルカプトベン
ゾイミダゾール、ウラゾール、チオウラシル、メ
ルカプトビリミジン、インダゾロン及びそれらの
誘導体の中から選ばれた少なくとも１種との組合
せを感光性成分としたポジ型感光性組成物を基板
上に塗布、乾燥したのち、活性光線を選択的に照
射し、現像することを特徴とするポジ型画像の形
成方法。1 (a) Compounds containing a quinonediazide group and (b) Mercaptooxazole, mercaptobenzoxazole, mercaptooxazoline, mercaptobenzothiazole, benzothiazolone, mercaptobenzimidazole, urazole, thiouracil, mercaptovirimidine, indazolone and derivatives thereof. A positive image characterized in that a positive photosensitive composition containing a combination of at least one selected photosensitive component as a photosensitive component is applied onto a substrate, dried, and then selectively irradiated with actinic rays and developed. How to form.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6500682A JPS58182633A (en) | 1982-04-19 | 1982-04-19 | Positive type photosensitive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6500682A JPS58182633A (en) | 1982-04-19 | 1982-04-19 | Positive type photosensitive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58182633A JPS58182633A (en) | 1983-10-25 |
| JPH0128935B2 true JPH0128935B2 (en) | 1989-06-06 |
Family
ID=13274467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6500682A Granted JPS58182633A (en) | 1982-04-19 | 1982-04-19 | Positive type photosensitive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58182633A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0658529B2 (en) * | 1983-08-17 | 1994-08-03 | 三菱化成株式会社 | Positive-type cresol lunovolak photoresist composition |
| JPS60125841A (en) * | 1983-12-12 | 1985-07-05 | Mitsubishi Chem Ind Ltd | Positive type photoresist composition |
| JPS61219951A (en) * | 1985-03-27 | 1986-09-30 | Japan Synthetic Rubber Co Ltd | Positive type radiation sensitive composition |
| JPH0650393B2 (en) * | 1985-07-30 | 1994-06-29 | 日本合成ゴム株式会社 | Positive-type radiation-sensitive composition |
| JPH0654389B2 (en) * | 1986-06-23 | 1994-07-20 | 日本合成ゴム株式会社 | Positive type radiation sensitive resin composition |
| JPH0654386B2 (en) * | 1986-03-28 | 1994-07-20 | 日本合成ゴム株式会社 | Positive type radiation sensitive resin composition |
| WO2008078622A1 (en) * | 2006-12-27 | 2008-07-03 | Konica Minolta Medical & Graphic, Inc. | Positive-working lithographic printing plate material and method for manufacturing lithographic printing plate using the positive-working lithographic printing plate material |
| JP5593678B2 (en) * | 2009-11-10 | 2014-09-24 | デクセリアルズ株式会社 | Quinonediazide photosensitizer solution and positive resist composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5747875A (en) * | 1980-09-02 | 1982-03-18 | Matsushita Electric Ind Co Ltd | Resist composition |
| JPS5748733A (en) * | 1980-09-08 | 1982-03-20 | Fuji Photo Film Co Ltd | Photosensitive lithographic plate |
-
1982
- 1982-04-19 JP JP6500682A patent/JPS58182633A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5747875A (en) * | 1980-09-02 | 1982-03-18 | Matsushita Electric Ind Co Ltd | Resist composition |
| JPS5748733A (en) * | 1980-09-08 | 1982-03-20 | Fuji Photo Film Co Ltd | Photosensitive lithographic plate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58182633A (en) | 1983-10-25 |
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